Use of inkjet-printing technique to create large area

OLED devices
Tommaso Rondini
February 20, 2024

1 Abstract
The organic light emitting diodes (OLEDs) are electroluminescence, current-controlled devices.
Their features, such as lightweight, high energy efficiency, high brightness, the possibility to
create thin and flexible devices, make them excellent technology in many uses. In the first part of
this study I reported an overview about the state of the art of OLEDs, summarizing some papers.
The most used are: Recent advances in efficient emissive materials-based OLED applications: a
review (2021) by Jayanta Bauri et al. [1], A review paper on: organic light-emitting diode (OLED)
technology and applications (2020) by Nikhil Sain et al. [2], and A survey of the structure,
fabrication, and characterization of advanced organic light emitting diodes (2023) by Debashish
Nayak et al. [3].
However, is there still an issue, which is to make their implementation cheaper and more
scalable to increase deployment. In the second part of this report I presented the results obtained
by Chandra Kant et al. about possibility to use inkjet-printing technique to develop large area
devices. Their results are in the paper: Large area inkjet-printed OLED fabrication with solution-
processed TADF ink [4] published November 9th , 2023.

2 Introduction
In a world that requires always more energy, we need more efficiency technologies, also for re-
duce the use of fossil flues. The 15 − 20% of electricity is used for illumination [5]. Since 2012
in European Union the incandescent light bulbs production has been forbidden [6] to reduce
electricity consumption and encourage the use of less energy-intense technologies. Using LED
and OLED lighting economized 50% electricity and 50% increase in output efficiency [7]. Nick
Holonyack reported the first practical LED with consulting engineer based on gallium arsenide
phosphide materials in the visible range in 1962. Then, Ching Tang and Steven Van Slyke re-
ported the first OLED at Kodak in 1987. Electroluminescence is the basic working principle of
both LED and OLED. OLEDs have certain distinct qualities that set them apart from LEDs, de-
spite their identical operating principle: OLEDs are built of organic semiconductor material that
generates light when voltage is applied, whereas LEDs are formed of inorganic semiconductors
and need backlights. LED has many limitations such as lower current density, lower lumines-
cence efficiency, lower lifetime, and lousy color quality of emission light at high temperatures [8].
On the other hand, an OLED is an exciting technology in luminescence science. The motive
for using organic polymers it that they extends conjugated free-electron systems for better effi-
ciency, flexibility, stability, etc. OLED displays have viewing angle of at ∼84°, wider than LED
ones. OLEDs are lighter than LEDs because their screens are thinner (since they do not need

1
backlight panel). OLEDs reply faster than LEDs because their diodes respond faster. Due to its
self-illumination, OLEDs use less electricity than LEDs. Hence, the organic semiconductor-based
OLED advances optoelectronic technology above the LED and have became the forefront next
generation flat-panel display [9]. OLEDs have advantages over LCD displays too: (i) very thin
solid-state device; (ii) lightweight: the substrates are shatter resistant unlike glass displays of
LCD devices; (iii) high luminous power efficiency: an inactive OLED element does not generate
light or consumes power, hence allowing true blacks; (iv) fast response time making entertaining
animations; (v) wide-viewing angle: OLEDs enable wider viewing angle in comparison to LCDs
because pixels in OLEDs emit light directly; (vi) self-emitting hence, removing requirement of a
backlight source; (vii) colour tuning for full colour displays; (viii) flexibility: OLED displays are
fabricated on flexible plastic substrates producing flexible organic LEDs; (ix) cost advantages
over inorganic devices: OLEDs are cheaper in comparison to LCD or plasma displays; (x) low
power consumption.

3 OLEDs’ characteristics
3.1 Working principle
The primary goal of OLED display technology is to precisely regulate and modify the electrical
current flowing through each pixel of the display or cell of the light source. OLEDs are current-
controlled devices, which means that the brightness of the output light is related to the amount
of current flowing
The base component of OLEDs is the emissive layer (EML), i.e. the organic electrolumines-
cence semiconductor. It is sandwiched between cathode and anode. The applied potential pulls an
electron from the HOMO level through the anode and throws into the LUMO level via cathode.
Opposite work is done in case of a hole; for this opposite charge separation, a strong electrostatic
potential is developed and this electrostatic force pulls each other into the active layer and forms
exciton. After the lifetime, this exciton releases energy as photon through a recombination pro-
cess. If this emitted photon is in the visible range, then it can be used as a lighting source or
display.
The exciton decay produces a photon only if it is in a singlet state: this phenomena is called
fluorescence. If it is in a triplet state, no photon is generated and the energy is lost as heat; it
is the phosphorescence. Statistically, only the 25% of the excitons are in singlet state, so a lot
of energy is lost and the OLED overheats. Adding some heavy metals (e.g. Pt, Ir or Os) the
triplet state excitons produce photons, so the efficiency increases (PHOLED). However, the use
of heavy metals increases cost and toxicity. The thermally activated delayed fluorescence (TADF)
organic semiconductors have an energy gap between singlet and triplet states so small that room
temperature energy allows transition from triplet to singlet states [10]. Hence some triple excitons
become singlet ones and produce photons; this phenomena is called reverse inter-system crossing
(RISC) [11] (Fig. 2 on page 5, part a).

3.2 Structures
The simplest and oldest structure of OLED is the single layer one: EML plus anode and cathode.
The EML must have strong hole and electron transport characteristics as well as excellent optical
efficiency.
It is not easy that a OSC has high electron and hole mobility, so it can be replaced with two
OSC: one with high hole mobility (hole transport layer or HTL) near anode, and one with high

2
electron mobility (electron transport layer or ETL) near cathode. In the interface between the
OSCs the excitons are formed.
In the three layers OLEDs, between HTL and ETL there is the EML, in which electrolumi-
nescence happens.
To avoid that electrons overcome the EML without creating excitons, electon blocking layer
(EBL) can be added between EML and HTL. This layer has a HOMO that allows hole to cross it
from HTL to EML, but a so high LUMO that electron can not cross it from EML to HTL. The
hole blocking layer (HBL) has the same purpose but about holes. In multilayer OLEDs (Fig. 1),
there are also injection electron layer (IEL) and injection hole layer (IHL) near cathode and
anode respectively. Their purpose is to facilitate the passage of charge carriers from electrodes.

Figure 1: Representation of work functions, HOMO and LUMO energy level of a multilayer OLED.
Image from [1]

3.3 Types
OLEDs are categorized according to light emission mechanism and operation techniques.
If the photons exit through the substrate side, or through the opposite side or through both,
the OLED is called respectively bottom, top, transparent-OLED. Obviously at least one side
must be transparent, otherwise we can not see light. Bottom and top-OLEDs have not great
differences and can be use to create displays, lighting sources, etc. Transparent-OLEDs can be
used in rear-view mirrors and transmitters or had-up information systems.
According to how each pixel or lighting cell is activated, OLED devices are spit in passive
matrix OLEDs (PMOLEDs) and active matrix OLEDs (AMOLEDs). In PMOLEDs, the elec-
trodes create a grid (anode creates columns and cathode creates row or vice versa) and in each
node there is only one pixel. In this way, polarizing the correct row and column we turn on the
related pixel. PMOLEDs are easy and cheap to create but use more power than other OLEDs

3
but still less power than LCD and LED. They are limited in size and resolution. In AMOLEDs,
the cathode is a whole panel. The anode is a thin film transistor (TFT) in parallel to form a
matrix, which helps in switching each pixel up to its on or off state as required, hence forming
an image. AMOLEDs are least power consuming type and have quick refresh rates.

4 Large area inkjet-printing OLEDs

4.1 Fabrication: large area inkjet-printed
OLEDs are created by depositing a thin film of electroluminescence OSC. The layer has to have
thickness as homogeneous as possible and smooth surface so that successive layer can be deposed
on it (e.g. HBL, ETL and cathode). It can be created with a lot of different techniques, that have
some pros and cons. Some very common techniques are the vacuum ones, that enable excellent
control over thickness and quality, but are very expensive, slow and difficult to employ to large
surfaces. Another method is the spin-coated one, where the material is put in the middle and
then, by rotation of the substrate, spread over all the surface. However, this method can not be
used for large surfaces, too.
The inkjet-printing (IJP) enables to create custom devices without masks or lithographies and
with excellent precision. Additionally, in contrast to vacuum deposition methods, almost all the
material is used, reducing waste. A number of issues need to be resolved to enable this technology
to be use on large scale: (i) solution processable low-cost triplet emitters; (ii) printing from non-
chlorinated green solvents; (iii) large-area printing in ambient conditions without compromising
the device performance; (iv) high-resolution patterning without the use of traditional lithography.
This requires emissive materials to be formulated into a stable ink with a suitable viscosity and
surface tension range, which has been a challenging task. The ideal ink should also provide a
smooth, uniform coating without thickness variation. Hence, low-cost ink formulation must be
developed for uniform jetting and optimal film formation for roll-to-roll printing.
In Chandra Kant et al. article of the 2023 [4] they developed ink formulation for a TADF
material and showed successful inkjet-printing of intricate patterns over large areas. They studied
the impact of ink viscosity, density and surface tension on the droplet formation and film quality.
In their work, they used as ink formulation 3-(9,9-dimethylacridin10(9H)-yl)-9H-xanthen-9-one
(ACRXTN) dispersed in 4,4’-bis-(n-carbazoly)-1,1’-biphenyl (CBP) host matrix, using a binary
solvent mixture of toluene and methyl benzoate (MB) (Fig. 2 b).

4.2 Results
4.2.1 Ink formulation of the emission layer
Once they have selected the ACRXTN as TADF material, the next step was to find the correct
solvent and the concentration. The solvent’s boiling point must not be too high (otherwise the
drop will not dry) neither too low (otherwise it evaporates in air-nozzle interface). The MB has
a relatively higher viscosity, higher boiling point and low vapour pressure to act as solvent alone.
To overcome these issues, toluene was selected as co-solvent: in this way the parameters are
in the ranges allowed by Fujifilm Dimatix Samba Cartridges (DMC-11610) used in this study.
Then, they checked different concentrations of TADF/CBP in toluene/MB (40:60): 5.5 mg mL−1 ,
11.25 mg mL−1 , 15 mg mL−1 and 20 mg mL−1 and the best was 11.25 mg mL−1 . In fact, smaller
concentrations create too thin films and greater concentrations do not result in stable inks.

4
Figure 2: a. Simplified Jablonski diagram of TADF route, showing electron-hole recombination. b.
Molecular structures of CBP, ACRXTN, TAPC, and PVK. Image from [4]

4.2.2 IJP on PEDOT:PSS films

They tried to print the ink on the hole injection layer of PEDOT:PSS, but the ink showed signif-
icant dewetting effects while drying. To overcome this issue, a PVK-TAPC blend thin film was
spin-coated in the PEDOT:PSS layer (Fig. 2 b). The thin film acts as electron blocking layer,
too. Drops were printed at 200 dots per inch (DPI) at three different substrate temperatures:
30 °C, 40 °C and 50 °C. The drying behaviours of the printed patterns (including drop diameter,
ink segregation, droplet shape upon impinging on the substrate, and deposit thickness profile)
were investigated using optical profilometer. Increasing temperature, the droplet diameter de-
creases because the drop dries faster and it has a M-shape, bell shape and mountain shape. The
M-shape is due to the coffee ring effect: the solvent evaporates faster on the edges and transports
the solute to the borders.

4.2.3 Print resolution on the film formation process

They made tests to understand how the result changes according to dots per inch (DPI). Changing
from 100 DPI to 800 DPI at 40 °C substrate temperature, they saw that below 400 DPI there
are discontinuity and over 600 DPI coffee ring was observed. Comparing linewidth, 800 DPI is
wider than 400 DPI of the 40% This shows that IJP can create uniform thin films by fine-
tuning the printing parameters. This uniformity is necessary for multilayer light-emitting devices,
demonstrating why this finding is significant.

4.2.4 IJP small area OLEDs

To study electroluminescence properties of the TADF ink, small area OLEDs were fabricated
on ITO-coated glass substrates. After performing an ozone surface treatment on ITO substrate,
they sequentially deposited PEDOT:PSS (40 nm) and PVK-TAPC blend (15 nm) using spin-
coating technique. Films were annealed at 120 °C for 15 min. The TADF ink was inkjet-printed
on PVK-TAPC blend film using an LP50-Pixdro industrialgrade inkjet-printer equipped with a
piezoelectric-driven 10 pL Dimatix cartridge (16 nozzles of 21 µm diameter). For direct compar-

5
ison, the same ink formulation was spin-coated on PVK-TAPC blend film. Both inkjet-printed
and spin-coated TADF films were annealed at 90 °C for 10 min under a nitrogen shower. The
substrates were then moved in a vacuum chamber, and TPBi (32 nm), calcium (20 nm), and
aluminium (100 nm) were sequentially evaporated by thermal evaporation at 5 × 10−6 torr.
Inkjet-printed OLEDs (IJP1, IJP2, and IJP3) with varying thicknesses were achieved by
changing the resolution (500 DPI, 600 DPI and 700 DPI respectively), while device SP1 was the
spin-coated TADF OLED (Fig. 3 a). They noted that increasing DPI (and so the thickness)
the brightness and the current efficiency decrease and the light turn-on voltage increases for IJP
devices. Table 1 summarizes device characteristics per each device.
To create anything other than a simple light source, patterning is essential. If we want to
pattern the electrodes we needed to deposit a dielectric layer on the substrate or lithographically
patterning an ITO electrode. Inkjet-printing approach does not require all these techniques:
it is sufficient to print the TADF material only in selected places. This method allows in-sito
patterning to be performed without requiring further fabrication steps. A 600 DPI IJP device
shows smooth emission and has sharp borders. However it has a faint brownish-pink background
hue. It is due to direct charge carrier recombination from TPBi to PVK-TAPC blend film (as
happened in the Wang et al. study [12]) (Fig. 3 b).

Table 1: Summary of characteristics of the fabricated devices with pixel area 4×4 mm2 : thickness of
the EML, voltage needing to activate the device; current efficiency at different brightness and maximal
brightness.

Devices Thickness Von CE (cd A−1 ) Lmax

(nm) (V) @ 100 cd m−2 @ 1000 cd m−2 (cd m−2 )
SP1 36 ± 2 3.9 ± 0.1 13.7 ± 0.8 7.6 ± 0.8 1775 ± 80
IJP1 25 ± 2 4.1 ± 0.1 12.4 ± 1.0 6.8 ± 0.5 2350 ± 40
IJP2 29 ± 2 4.2 ± 0.1 7.5 ± 2.7 6.0 ± 0.2 2060 ± 90
IJP3 33 ± 3 4.3 ± 0.1 9.5 ± 0.4 6.9 ± 0.6 1985 ± 10

Figure 3: a. An operational inkjet-printed TADF OLED biased at 6.0 V emission of cyan colour light
with an active area of 4×4 mm2 , and an inset image of the same pixel at a lower voltage bias (4.5 V). b.
An inkjet patterned OLED with texts of “AISRF OLED” on 37×37 mm2 area in a room light (biased at
5.0 V), whereas the inset image of letter ‘E’ shows the sharp edges of printed patterns. Image from [4]

6
4.2.5 IJP large area OLEDs
To demonstrate large area ink-jet printed (LAiP) OLEDs, they fabricated large-area panel
IJP TADF OLEDs on 120×120 mm2 chromium/ITO/glass substrates with an active area of
80×80 mm2 in a 10, 000-class clean room at ambient conditions (Fig. 4 c). They applied the
chromium grid for the homogeneous current distribution as the sheet resistance of ITO starts
to affect the large-area substrates. After performing an ozone surface treatment of the ITO sub-
strate, PEDOT:PSS and PVK-TAPC layers were spin-coated on top. To avoid introduction of
dust that would cause short circuit, substrate annealing was performed under N2 shower. Sub-
strates were then annealed at 120 °C for 15 min before the TADF ink was IJP at 600 DPI on
top of the PVK-TAPC layer. This gave a device structure of ITO/PEDOT:PSS (40 nm)/PVK-
TAPC (18 nm)/TADF (30 nm)/TPBi (32 nm)/Ca (20 nm)/Al (100 nm). The devices were then
encapsulated for characterization and analysis.
They noticed some non-uniformities of light emission at the lower voltages but they dis-
appeared as the bias voltage increased (Fig. 4 c). This may be due to non-uniformity of the
spin-coated layers (PEDOT:PSS and PVK-TAPC) on a large substrate area. The LAiP OLED
had the maximum current efficiency of 13.7 cd A−1 @ 622 cd m−2 , which is close to those of
spin-coated small area OLEDs.
To create a large area patterned OLED they inkjet-printed photoresist dielectric to create
the desired intricate template on ITO substrate (Fig. 4 b). Then it was exposed with UV light
to cross-link the photoresist and all the other procedures were attended. The device achieved
brightness of 500 cd m−2 at 10 V. The images show high contrast glowing edges and the dielectric
layer eliminates direct charge recombination from TPBi to PVK-TAPC regions (Fig. 4 d).

5 Discussion
They developed large-area multilayer OLEDs with an inkjet-printed TADF emission layer. They
successfully demonstrated IJP as a single-step maskless emission layer patterning technique, to
create intricate and high-resolution designs for signage, wearable electronics, and advertising
without the use of typical lithographically steps. They achieved stable ink formulation using
non-chlorinated binary solvent mixture of toluene:MB in combination with a suitable quantity of
TADF and CBP. This technique allows to create devices in a cheap, green, scalable and roll-to-roll
implementable way, that yields OLED more interesting technology.

7
Figure 4: a. Handheld large-area panel substrate (120×120 mm2 ) with an active area of 80×80 mm2
through square chromium grid. b. Inkjet patterned large area logos on a 100×100 mm2 substrate, con-
sisting of The University of Queensland and IIT Kanpur with two rectangular strips of 10×70 mm2 and
5×70 mm2 before the thermal evaporation of other layers. c. The LAiP OLED (120×120 mm2 ) operated
at 10.5 V with an inset image at 6 V. d. The LAiP (100×100 mm2 ) intricate logo OLED biased at 10 V
with brightness of ∼500 cd m−2 . Brightness measured at the rectangular strip. Image from [4]

8
References
[1] Jayanta Bauri, Ram Bilash Choudhary, and Gobind Mandal. “Recent advances in efficient
emissive materials-based OLED applications: a review”. In: Journal of Materials Science
56.34 (Dec. 2021), pp. 18837–18866. doi: 10.1007/s10853-021-06503-y.
[2] Nikhil Sain, Deepesh Sharma, and Priya Choudhary. “A review paper on: organic light-
emitting diode (OLED) technology and applications”. In: International Journal of Engi-
neering Applied Sciences and Technology 04 (Apr. 2020), pp. 587–591. doi: 10.33564/
IJEAST.2020.v04i11.103.
[3] Debashish Nayak and Ram Bilash Choudhary. “A survey of the structure, fabrication, and
characterization of advanced organic light emitting diodes”. In: Microelectronics Reliability
144 (2023), p. 114959. issn: 0026-2714. doi: https://doi.org/10.1016/j.microrel.
2023.114959.
[4] Chandra Kant et al. “Large area inkjet-printed OLED fabrication with solution-processed
TADF ink”. In: Nature Communications 14.1 (Nov. 2023), p. 7220. issn: 2041-1723. doi:
10.1038/s41467-023-43014-7.
[5] Yuan-Sheng Tyan. “Organic light-emitting-diode lighting overview”. In: Journal of Photon-
ics for Energy 1.1 (2011), p. 011009. doi: 10.1117/1.3529412.
[6] Member States approve the phasing-out of incandescent bulbs by 2012. 2008. url: https:
//ec.europa.eu/commission/presscorner/detail/en/IP_08_1909.
[7] N. Thejo Kalyani and S.J. Dhoble. “Organic light emitting diodes: Energy saving light-
ing technology—A review”. In: Renewable and Sustainable Energy Reviews 16.5 (2012),
pp. 2696–2723. issn: 1364-0321. doi: https://doi.org/10.1016/j.rser.2012.02.021.
[8] Wolfgang Brütting, Stefan Berleb, and Anton G. Mückl. “Device physics of organic light-
emitting diodes based on molecular materials”. In: Organic Electronics 2.1 (2001), pp. 1–
36. issn: 1566-1199. doi: https://doi.org/10.1016/S1566-1199(01)00009-X.
[9] Qiang Su, Heng Zhang, and Shuming Chen. “Flexible and tandem quantum-dot light-
emitting diodes with individually addressable red/green/blue emission”. In: npj Flexible
Electronics 5.1 (Mar. 2021), p. 8. issn: 2397-4621. doi: 10.1038/s41528-021-00106-y.
[10] Hajime Nakanotani, Youichi Tsuchiya, and Chihaya Adachi. “Thermally-activated Delayed
Fluorescence for Light-emitting Devices”. In: Chemistry Letters (2021). url: https : / /
api.semanticscholar.org/CorpusID:234004176.
[11] Jong Uk Kim et al. “Nanosecond-time-scale delayed fluorescence molecule for deep-blue
OLEDs with small efficiency rolloff”. In: Nature Communications 11.1 (Apr. 2020), p. 1765.
doi: 10.1038/s41467-020-15558-5.
[12] Jiong Wang et al. “Highly efficient solution-processed red phosphorescent organic light-
emitting diodes employing an interface exciplex host”. In: J. Mater. Chem. C 8 (29 2020),
pp. 9909–9915. doi: 10.1039/D0TC00893A.